CN-117510311-B - Preparation method of novel anionic short-branched polyol polyoxypropylene ether carboxylate surfactant

Abstract

The present invention discloses a method for preparing a novel anionic short branched polyol polyoxypropylene ether carboxylate surfactant. The method uses short branched polyol (3,8-dimethyl-1,4,7,10-decantetraol) and epichlorohydrin (PO) ring opening polymerization, and then selects precious metal (Pd/C) catalytic oxidation to prepare short branched polyol polyoxypropylene ether carboxylate surfactant. The product has good wetting and foaming properties, and can be further applied as a compatibilizer and plasticizer in packaging plastic raw materials to improve the plasticity of brittle materials and the compatibility between blended materials.

Inventors

• LUO WENHAN
• ZHAN WEIZHAO
• XIAO NAIYU
• WANG LIANGBIN

Assignees

• 仲恺农业工程学院
• 茂名绿色化工研究院

Dates

Publication Date

20260512

Application Date

20231031

Claims (3)

1. 1. The preparation method of the novel anionic short-chain branched polyol polyoxypropylene ether carboxylate surfactant is characterized by comprising the following steps of: (1) Adding 3, 8-dimethyl-1, 4,7,10 decane tetraol and potassium hydroxide into a clean and dry reaction kettle, sealing, replacing the reaction kettle with N 2 for three times, removing air in the kettle, heating to 115-135 ℃, stirring all the time, starting a vacuum pump, vacuumizing and dehydrating for 20-30 min, slowly adding propylene oxide into the reaction kettle in a nitrogen environment, reacting for 10-20 min at constant temperature and constant pressure, cooling to 70-90 ℃ after the reaction is completed, adding glacial acetic acid for neutralization to neutrality, preserving heat for 30min, cooling, and obtaining the novel short-chain polyol ether by N 2 extrudate; (2) Adding the novel short-chain branched polyol ether obtained in the step (1) and a noble metal Pd/C catalyst, sodium hydroxide and water into a reaction kettle, introducing O 2 into the reaction system, keeping the constant temperature at 110-120 ℃, continuously stirring for 8-10 hours, centrifugally separating after the reaction is finished, pouring the liquid into a flask, adding concentrated sulfuric acid to adjust the pH value to 1-2, removing residual sodium hydroxide, and washing with water to obtain the novel anionic short-chain branched polyol polyoxypropylene ether carboxylic acid surfactant; In the step (1), the volume ratio of the 3, 8-dimethyl-1, 4,7, 10-decanetetraol to the propylene oxide is 1:3-5.
2. 2. The method for preparing the novel anionic short-chain branched polyol polyoxypropylene ether carboxylate surfactant according to claim 1, wherein in step (1), propylene oxide is slowly added into the reaction kettle within 1 h.
3. 3. The method for preparing a novel anionic short-chain branched polyol polyoxypropylene ether carboxylate surfactant according to claim 1, wherein the amount of noble metal Pd/C catalyst and 3, 8-dimethyl-1, 4,7, 10-decanetetraol used in step (2) is 5 g/100 mL.

Description

Preparation method of novel anionic short-branched polyol polyoxypropylene ether carboxylate surfactant Technical Field The invention belongs to the technical field of preparation of novel surfactants, and particularly relates to a preparation method of a novel surfactant of anionic short-chain branched polyol polyoxypropylene ether carboxylate. Background Alcohol Ether Carboxylate (AEC) is a novel surfactant with double properties of anions and non-ions, has various excellent characteristics such as good mildness, wettability, hard water resistance, good compatibility, easiness in biodegradation and the like, and is a currently accepted functional environment-friendly surfactant. Therefore, it can be widely used in cosmetics, industrial and household cleaning agents, metal processing fluids, biochemistry, textile auxiliaries, plastics, leather, pharmacy, petroleum industry, food processing and other industries. Structurally, it is classified as acid form R (CH 2CH2O)nOCH2 COOH Salt type R (CH 2CH2O)nOCH2 COOM) Very similar to the structural formula (RCOOM) of the soap, namely, EO/PO groups are embedded between lipophilic groups and hydrophilic groups, so that the soap has variable alkyl chain length and different ethoxylation degree and propoxylation degree, the defect of poor hard water resistance of the soap is overcome, and the advantage that the soap cannot be foamed vigorously is maintained. In the current patent research, the vast majority is two methods for synthesizing AEC by using the existing fatty Alcohol Ether (AEO) series on the market. The first is a carboxymethylation method, the representative patent is CN201510455671.1, which describes that alcohol ether and sodium chloroacetate are prepared in the presence of alkali metal hydroxide and a phase transfer catalyst, the alcohol ether and the phase transfer catalyst are put into a reactor, the alkali metal hydroxide and the sodium chloroacetate are mixed uniformly and then put into the reactor in batches, absolute ethyl alcohol is added after continuous curing, inorganic salt and excessive sodium chloroacetate are removed by filtration, and alcohol ether carboxylate is prepared after the absolute ethyl alcohol is removed by distillation. Although the method is simple and convenient to operate and has higher conversion rate, the problem of byproduct residues with adverse effects on human bodies is difficult to fundamentally solve, so that the application field of products is restricted, especially the application field of high-value-added high-end surfactants such as personal care products and the like, and the defects are almost defects which cannot be overcome by the production process of a carboxymethylation method. Secondly, noble metal oxidation, the representative patent is CN101357333A, describes that alkaline earth metal and transition metal are added into Pd/C catalyst as auxiliary components to improve the catalyst performance, and alcohol ether carboxylic acid is obtained by direct catalytic oxidation based on AEO series. The catalytic oxidation method is that the terminal hydroxymethyl of the fatty alcohol-polyoxyethylene ether is oxidized into carboxyl in the presence of a noble metal catalyst. The catalytic oxidation method has the characteristics of environmental friendliness, has the advantages of short process flow, low equipment requirement, capability of being used for continuous production, capability of preparing high-purity products and the like, and is characterized in that a proper catalyst is selected and prepared. Disclosure of Invention The invention aims to provide a preparation method of a novel anionic short-branched polyol polyoxypropylene ether carboxylate surfactant, which adopts ring-opening polymerization of short-branched tetraol and propylene oxide, and prepares alcohol ether carboxylate by catalytic oxidation of noble metal (Pd/C), and the prepared product has larger wetting property and foaming property. The aim of the invention can be achieved by the following technical scheme that the preparation method of the novel anionic short-chain branched polyol polyoxypropylene ether carboxylate surfactant comprises the following steps: (1) Adding 3, 8-dimethyl-1, 4,7, 10-decanetetraol and potassium hydroxide into a clean and dry reaction kettle, sealing, replacing the reaction kettle with N 2 for three times, removing air in the kettle, heating to 115-135 ℃, stirring all the time, starting a vacuum pump, vacuumizing and dehydrating for 20-30 min, slowly adding propylene oxide into the reaction kettle in a nitrogen environment, reacting for 10-20 min at constant temperature and constant pressure, cooling to 70-90 ℃ after the reaction is completed, adding glacial acetic acid for neutralization to neutrality, preserving heat for 30min, cooling, and obtaining the novel short-chain polyol ether by N 2 extrudate; (2) Adding the novel short-chain branched polyol ether obtained in the step (1) and a noble metal Pd/C cata